Effect of complex inhibitors containing ionic liquids and PVP K90 on formation of methane hydrate

REN Junjie; LONG Zhen; LIANG Deqing

doi:10.11949/0438-1157.20200342

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Effect of complex inhibitors containing ionic liquids and PVP K90 on formation of methane hydrate

Energy and environmental engineering | 更新时间：2026-07-24

- Effect of complex inhibitors containing ionic liquids and PVP K90 on formation of methane hydrate
- CIESC Journal Vol. 71, Issue 11, Pages: 5256-5264(2020)
- 作者机构：
  
  1.中国科学院广州能源研究所，广东广州 510640
  2.中国科学院天然气水合物重点实验室，广东广州 510640
  3.广东省新能源和可再生能源研究开发与应用重点实验室，广东广州 510640
  4.中国科学院广州天然气水合物研究中心，广东广州 510640
  5.天然气水合物国家重点实验室，北京100028
  6.中国科学院大学，北京 100049
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20200342
  CLC： TK 123
- Received：31 March 2020，
  
  Revised：2020-06-02，
  
  Online First：03 November 2020，
  
  Published：05 November 2020
- 稿件说明：
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任俊杰, 龙臻, 梁德青. 离子液体与PVP K90复合抑制剂对甲烷水合物的生成影响[J]. 化工学报, 2020, 71(11): 5256-5264

REN Junjie, LONG Zhen, LIANG Deqing. Effect of complex inhibitors containing ionic liquids and PVP K90 on formation of methane hydrate[J]. CIESC Journal, 2020, 71(11): 5256-5264
任俊杰, 龙臻, 梁德青. 离子液体与PVP K90复合抑制剂对甲烷水合物的生成影响[J]. 化工学报, 2020, 71(11): 5256-5264 DOI： 10.11949/0438-1157.20200342.

REN Junjie, LONG Zhen, LIANG Deqing. Effect of complex inhibitors containing ionic liquids and PVP K90 on formation of methane hydrate[J]. CIESC Journal, 2020, 71(11): 5256-5264 DOI： 10.11949/0438-1157.20200342.

摘要

注入抑制剂是油气行业解决管道输送过程因水合物生成而引发的堵塞问题最常用的方法。但现有大多数动力学抑制剂（KHIs）存在抑制性能不足、高过冷度条件下会失效等问题，可应用场合大大受限。离子液体作为绿色溶剂对甲烷水合物具有良好的热力学抑制作用。为改进KHIs的性能，提出将离子液体与KHIs复合。本文实验考察8.0 K过冷度、两种浓度下[1.0%(质量)、2.0%(质量)

]

离子液体

-丁基-

-甲基吡咯烷四氟硼酸盐([BMP

]

[BF

]

)、聚乙烯基吡咯烷酮（PVP K90）以及二者复配构成的复合型抑制剂对甲烷水合物抑制规律，得到了最佳组分配比。利用粉末X射线衍射（PXRD）和低温激光拉曼光谱测量了不同抑制剂体系中形成的甲烷水合物晶体微观结构和晶穴占有率，发现添加抑制剂不会改变sI型甲烷水合物晶体结构，但会影响水合物晶体的大、小笼占有率和水合数。结合宏观动力学实验和微观结构测试结果，揭示离子液体与PVP K90复合抑制剂的抑制机理。

Abstract

Injecting inhibitors is the most commonly used method in the oil and gas industry to solve the problem of blockage caused by hydrate formation during pipeline transportation. However

most of the kinetic hydrate inhibitors (KHIs) are strictly limited by weak inhibition performance and low subcooling. Ionic liquids

a kind of green solvent

have been recognized to act as excellent thermodynamic inhibitors on met

hane hydrate formation. So

it is proposed to add the ionic liquids into KHIs to improve their overall performance. In this paper

the kinetic effects of an ionic liquid

-butyl-

-methylpyrrolidine tetrafluoroborate ([BMP

]

[BF

]

)

a commercial kinetic inhibitor polyvinyl pyrrolidone (PVP K90) and their mixtures with different mass ratios on the methane hydrate formation were experimentally studied at 8.0 K subcooling and two concentrations [1.0%(mass) and 2.0%(mass)

]

. The best mass ratio of the compound inhibitor was determined. Moreover

the crystal structures and cage occupancy characteristics of methane hydrates formed without and with inhibitors at different mass concentrations and composition ratios were measured by using powder X-ray diffraction (PXRD) and low-temperature Laser Raman spectrometers. It was found that the addition of inhibitors did not change the crystal structure of methane hydrate

but affected the cage occupancies and hydration numbers. Based on the results from macroscopic kinetics and microscopic structure tests

the inhibition mechanism of compound inhibitors was proposed.

关键词

Keywords

references

Sloan E D , Koh C A . Clathrate Hydrates of Natural Gases [M ] . 3rd ed . Boca Raton : CRC Press , 2007 : 1 - 17 .

Wang Y H , Fan S S , Lang X M . Reviews of gas hydrate inhibitors in gas-dominant pipelines and application of kinetic hydrate inhibitors in China [J ] . Chinese Journal of Chemical Engineering , 2019 , 27 ( 9 ): 2118 - 2132 .

樊栓狮 , 郭凯 , 王燕鸿 , 等 . 天然气水合物动力学抑制剂性能评价方法的现状与展望 [J ] . 天然气工业 , 2018 , 38 ( 9 ): 103 - 113 .

Fan S S , Guo K , Wang Y H , et al . Present situation and prospect of performance evaluation methods for kinetic hydrate inhibitors (KHIs) [J ] . Natural Gas Industry , 2018 , 38 ( 9 ): 103 - 113 .

唐翠萍 , 戴兴学 , 梁德青 , 等 . 低剂量抑制剂Inhibex501存在下的甲烷水合物相平衡研究 [J ] . 新能源进展 , 2018 , 6 ( 1 ): 42 - 46 .

Tang C P , Dai X X , Liang D Q , et al . Equilibrium conditions for methane hydrate in the presence of low-dosage hydrate inhibitors aqueous solutions [J ] . Advances in New and Renewable Enengy , 2018 , 6 ( 1 ): 42 - 46 .

Bavoh C B , Partoon B , Lal B , et al . Inhibition effect of amino acids on carbon dioxide hydrate [J ] . Chemical Engineering Science , 2017 , 171 : 331 - 339 .

Ke W , Svartaas T M , Abay H K . An experimental study on sⅠ hydrate formation in presence of methanol , PVP and PVCap in an isochoric cell [C ] // Icgh 2011 . ICGH , 2011 : 17 - 21 .

Ke W , Kelland M A . Kinetic hydrate inhibitor studies for gas hydrate systems: a review of experimental equipment and test methods [J ] . Energy and Fuels , 2016 , 30 ( 12 ): 10015 - 10028 .

Talaghat M R . Experimental investigation of induction time for double gas hydrate formation in the simultaneous presence of the PVP and L-tyrosine as kinetic inhibitors in a mini flow loop apparatus [J ] . Journal of Natural Gas Science and Engineering , 2014 , 19 : 215 - 220 .

Schicks J M , Ripmesster J A . The coexistence of two different methane hydrate phases under moderate pressure and temperature conditions: kinetic versus thermodynamic products [J ] . Angewandte Chemie - International Edition , 2004 , 43 ( 25 ): 3310 - 3313 .

Anderson B J , Tester J W , Borghi G P , et al . Properties of inhibitors of methane hydrate formation via molecular dynamics simulations [J ] . Journal of the American Chemical Society , 2005 , 127 ( 50 ): 17852 - 17862 .

Kelland M A . History of the development of low dosage hydrate inhibitors [J ] . Energy and Fuels , 2006 , 20 ( 3 ): 825 - 847 .

Kim J , Shin K , Seo Y , et al . Synergistic hydrate inhibition of monoethylene glycol with poly(vinylcaprolactam) in thermodynamically underinhibited system [J ] . Journal of Physical Chemistry B , 2014 , 118 ( 30 ): 9065 - 9075 .

Chua P C , Kelland M A . Tetra( iso -hexyl)ammonium bromide - the most powerful quaternary ammonium-based tetrahydrofuran crystal growth inhibitor and synergist with polyvinylcaprolactam kinetic gas hydrate inhibitor [J ] . Energy and Fuels , 2012 , 26 ( 2 ): 1160 - 1168 .

Xu S R , Fan S S , Fang S T , et al . Excellent synergy effect on preventing CH 4 hydrate formation when glycine meets polyvinylcaprolactam [J ] . Fuel , 2017 , 206 : 19 - 26 .

Young W D , Cohen J M , Wolf P F . Enhanced hydrate inhibitors: powerful synergism with glycol ethers [J ] . ACS Division of Fuel Chemistry , Preprints , 1997 , 42 ( 2 ): 503 - 506 .

Xiao C W , Adidharma H . Dual function inhibitors for methane hydrate [J ] . Chemical Engineering Science , 2009 , 64 ( 7 ): 1522 - 1527 .

Xiao C W , Wibisono N , Adidharma H . Dialkylimidazolium halide ionic liquids as dual function inhibitors for methane hydrate [J ] . Chemical Engineering Science , 2010 , 65 ( 10 ): 3080 - 3087 .

Villano L D , Kelland M A . An investigation into the kinetic hydrate inhibitor properties of two imidazolium-based ionic liquids on structure II gas hydrate [J ] . Chemical Engineering Science , 2010 , 65 ( 19 ): 5366 - 5372 .

Kim K S , Kang J W , Kang S P . Tuning ionic liquids for hydrate inhibition [J ] . Chemical Communications , 2011 , 47 ( 22 ): 6341 - 6343 .

Lee W , Shin J Y , Kin K S , et al . Synergetic effect of ionic liquids on t he kinetic inhibition performance of poly( N -vinylcaprolactam) for natural gas hydrate formation [J ] . Energy and Fuels , 2016 , 30 ( 11 ): 9162 - 9169 .

Lee W , Shin J Y , Kim K S , et al . Kinetic promotion and inhibition of methane hydrate formation by morpholinium ionic liquids with chloride and tetrafluoroborate anions [J ] . Energy and Fuels , 2016 , 30 ( 5 ): 3879 - 3885 .

Shen X D , Zhou X B , Liang D Q . Kinetic effects of ionic liquids on methane hydrate [J ] . Energy and Fuels , 2019 , 33 ( 2 ): 1422 - 1432 .

Coquelet C , Chapoy A , Richon D . Development of a new alpha function for the Peng-Robinson equation of state: comparative study of alpha function models for pure gases (natural gas components) and water-gas systems [J ] . International Journal of Thermophysics , 2004 , 25 ( 1 ): 133 - 158 .

Peng D Y , Robinson D B . A new two-constant equation of state [J ] . Industrial and Engineering Chemistry Fundamentals , 1976 , 15 ( 1 ): 59 - 64 .

Sangwai J S , Oellrich L . Phase equilibrium of semiclathrate hydrates of methane in aqueous solutions of tetra- n -butyl ammonium bromide (TBAB) and TBAB-NaCl [J ] . Fluid Phase Equilibria , 2014 , 367 : 95 - 102 .

Gayet P , Dicharry C , Marion G , et al . Experimental determination of methane hydrate dissociation curve up to 55 MPa by using a small amount of surfactant as hydrate promoter [J ] . Chemical Engineering Science , 2005 , 60 ( 21 ): 5751 - 5758 .

Nixdorf J , Oellrich L R . Experimental determination of hydrate equilibrium conditions for pure gases, binary and ternary mixtures and natural gases [J ] . Fluid Phase Equilibria , 1997 , 139 ( 1/2 ): 325 - 333 .

Zhou X B , Long Z , Liang S , et al . In situ Raman analysis on the dissociation behavior of mixed CH 4 -CO 2 Hydrates [J ] . Energy and Fuels , 2016 , 30 ( 2 ): 1279 - 1286 .

Wang J W , Lu H L , Ripmeester J A . Raman spectroscopy and cage occupancy of hydrogen clathrate hydrate from first-principle calculations [J ] . Journal of the American Chemical Society , 2009 , 131 ( 40 ): 14132 - 14133 .

Schober H , Itoh H , Klapproth A , et al . Guest-host coupling and anharmonicity in clathrate hydrates [J ] . European Physical Journal E , 2003 , 12 ( 1 ): 41 - 49 .

周雪冰 , 刘婵娟 , 罗金琼 , 等 . 甲烷水合物分解过程的微尺度测量 [J ] . 化工学报 , 2019 , 70 ( 3 ): 1042 - 1047 .

Zhou X B , Liu C J , Luo J Q , et al . Microscopic measurements on methane hydrate dissociation [J ] . CIESC Journal , 2019 , 70 ( 3 ): 1042 - 1047 .

Lu H L , Moudrakovski I , Riedel M , et al . Occurrence and structural characterization of gas hydrates associated with a cold vent field, offshore Vancouver Island [J ] . Journal of Geophysical Research: Solid Earth , 2005 , 110 ( 10 ): 1 - 9 .

Uchida T , Hirano T , Ebinuma T , et al . Raman spectroscopic determination of hydration number of methane hydrates [J ] . AIChE Journal , 1999 , 45 ( 12 ): 2641 - 2645 .

Li Z , Jiang F , Qin H B , et al . Molecular dynamics method to simulate the process of hydrate growth in the presence/absence of KHIs [J ] . Chemical Engineering Science , 2017 , 164 : 307 - 312 .

Cheng L W , Liao K , Li Z , et al . The invalidation mechanism of kinetic hydrate inhibitors under high subcooling conditions [J ] . Chemical Engineering Science , 2019 , 207 : 305 - 316 .

Kvamme B , Huseby G , Forrisdahl O K . Molecular dynamics simulations of PVP kinetic inhibitor in liquid water and hydrate/liquid water systems [J ] . Molecular Physics , 1997 , 90 ( 6 ): 979 - 992 .

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